Di-(nitrodiphenylaminesulfonamido)compounds

ABSTRACT

WATER INSOLUBLE COMPOUNDS PREPARED BY CONDENSING THE PRODUCT OF A NITROCHLLOROBENZENE AND A DIAMINE WITH AN ANILINE COMPOUND ARE USEFUL AS DYES FOR HYDROPHOBIC TEXTILE MATERIALS.

r 3,729,493 Ice Patented Apr. 24, 1973 3,729,493 DI.-(NITRODIPHENYLAMINESULFONAMIDO) COMPQUNDS David H. Wilcox, Jr., Kingsport, Tenn., assiglnor to )n Eastman Kodak Company, Rochester, 5 wherein X represents lower alkyl, e.g. having up to about No Drawmg' i 7 672,709 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, Us Cl g' c 10 Claims butyl; lower alkoxy, e.g. having up to about 4 carbon atoms such as methoxy, ethoxy, butoxy; lower alkanoylamino, e.g. acetamido, propionamido; halogen, e.g. chloro, ABSTRACT OF E DISCLOSURE 10 bromo; lower alkylsulfonyl, e.g. methylsulfonyl, butyl- Water insoluble compounds prepared by condensing sulfonyl; Substituted lower alkylslllfenyl, Such as y the product of a nitrochlorobenzene and a diamine with alkyisuifonyl; lower alkoxyearbonyl, methoXyeafan aniline compound are useful as dyes for hydrophobic bonyl, ethoXycarbonYL butoXyearbonyl; earbamoy],

lower alkylcarbamoyl, e.g. N-methylcarbamoyl, N,N-dilower alkylcarbamoyl, e.g. N,N-diethylcarbamoyl; phenyl; benzamido; lower alkanoyl, e.g. acetyl, propionyl, butyryl; sulfamoyl, N- and N,N-d'i-lower alkylsulfamoyl, e.g. N- propylsulfamoyl, N,N-diethylsulfamoyl, lower alkylsulfonamido, e.g. methylsulfonamido, ethylsulfonamido; thiocyanato; and lower alkylthio, e.g. methylthio, propylthio, and n represents 1, 2, or 3. When n is more than 1, R3 the substituents represented by X can be the same or I different. R HN SO2NHR1 NHsO2 TNEPR: Methyl, ethyl, propyl, isopropyl, etc., are typical alkyl groups which R and R can represent. Methylene, ethyl- NO2 ene, propylene, isopropylene, butylene, isobutylene, wherein amylene, hexamethylene, etc., are examples of the alkylene groups which R can represent. Illustrative of the cyclohexylene groups that R can represent are 1,4-cyclohexylene, 1,2-cyclohexylene, and 4-methyl-l,3-cyclohexylene. 1,4-cyclohexylenedimethylene, 1,3-cyclohexylenedimethylene, and 1,Z-cyclohexylenediethylene are examples of the cyclohexylenedialkylene groups represented by R textile materials.

This invention relates to novel water-insoluble di(phenylaminonitrophenyl'sulfonamido) compounds, which are useful as dyes for hydrophobic textile materials.

The compounds of the invention have the general formula R and R each represent a phenyl radical;

R represents alkylene, cyclohexylene, lower alkylcyclohexylene, cyclohexylenedialkylene, or a phenylene radical; and

R and R each represent hydrogen or lower alkyl.

' The nitrodiphenylamine compounds of the invention Th phenylene radical which 1 can represent can be give Yellow dyeings having high tineteriai Properties and unsubstituted 0rtho-, meta-, or para-phenylene or sub- XC ll Sublimation fastness When pp to y stituted phenylene such as, for example, lower alkylphenphobic textile fibers, yarns and fabrics by conventional ylene, 3- h 1-1 4- h 1 lower lk h l. means. Fastness to sublimation is of particular importance ene, e.g. 2-methoxy-1,4-phenylene; halogen, e.g 3-b in the dyeing of polyester fibers by the heat fixation technique during which the dye is submitted totemperatures 1,4-phenylene, 2-methoxy-6-chloro-1,3-phenylene; etc.

40 A particularly preferred group of the compounds of as high as 410 C. Cellulose acetate, polyamid'e and polyth inventi nfor to the f rmula NHSOzHN-(CH2h-NHSOz-Q-NH-Q X l ioz l lo: X ester fibers are illustrative of the hydrophobic textile whereinXrepresents hydrogen, lower alkyl, lower alkoxy, materials which can be dyed with the compounds of the or halogen and m is 2 or 3. invention. The compounds of the invention are water The compounds of the invention are prepared by reinsoluble and therefore can be applied to hydrophobic acting approximately 2 moles of a 3-nitro-4-chlorobentextile materials by methods well known in the art of diszenesulfonyl chloride with about 1 mole of a diamine perse dyes. Coloration of such textile materials can also having the formula H N--R NH wherein R is debe effected by incorporating the novel compounds into fined above, to obtain an intermediate di-(4-chloro-3- the dope or melt prior to spinning and then spinning the nitrophenylsulfonamido) compound. About one mole of fiber as usual. the intermediate compound is then reacted with an aniline Illustrative of the groups represented by R and R are compound having the formula R NH and/or R -NH phenyl, p-nitrophenyl, p-chlorophenyl, o-chloro-p-nitroto obtain the compounds of the invention. It is apparent phenyl, 0-methylsulfonyl-p-nitrophenyl, 2,6-dichloro-4 that by reacting equimolar quantities of the intermediate nitrophenyl, p-acetylphenyl, p-cyanophenyl, p-tolyl, pcompound and an aniline compound followed by the anisyl, p-sulfamoylphenyl, p-acetamidophenyl, o,p-direaction of the resulting compound with a different aniline methylsulfonylphenyl, 2,4 dinitro-6-chlorophenyl, pcompound, unsymmetrical compounds can be obtained. ethoxycarbonylphenyl, p-trifiuoromethylphenyl, p-methyl- Those Skilled in the art Will recognize that there are sulfonylphenyl, etc. A preferred group of the substituted other methods y Which the mp s of e invention phenyl radicals which R and R can represent have the can be prepared.

formula The diamines and anilines useful in preparing the com- 4 pounds of the invention are well-known and are commer- 18 hours. The mixture is then cooled to 20 C., filtered cially available or can be prepared according to published and the yellow-orange filter cake is washed until alkalitechniques. free and dried. A yield of 59 grams of yellow dye is ob- The following examples will serve to illustrate the prepatained. It has the formula:

Q-NHQ-SOzNHC;H NHSOz--NH NO: 1 102 ration of representative intermediates and nitrodiphenyl- 1 It colors cellulose acetate, polyester, and polyamide textile amine compounds of the invention. material yellow shades of good sublimation fastness.

EXAMPLE 1 EXAMPLE 4 To a solution of 12 grams of ethylenediamine and 67.2 In 200 ml. of water are dissolved one gram of sodium grams of sodium bicarbonate dissolved in 400 ml. of water ligninsulfonate, 52.1 grams of 3-nitro-4-chlorobenzenesulat 40 C., 108.4 grams of 3-nitro-4-chlorobenzenesulfonyl fonyl chloride (95 assay), and 16.8 grams of sodium chloride (90% assay) is added portionwise. The reaction bicarbonate. Then, 17.8 grams of 1,3-diaminobutane is mixture is then heated to 60-65 C. for two hours, cooled added and the mixture is heated at 65-70 C. for two to 15 C. and filtered. The filter cake is washed with water hours. The mixture is then cooled to C., the mother and slurried in a mixture of 80 ml. isopropanol and 160 liquor is decanted and the insoluble material is dissolved ml. water. Then, 16.8 grams of sodium bicarbonate, 36 in 70 ml., of hot isopropanol. The mixture is diluted with grams of aniline and 10 drops of piperidine are added and 140 ml. of water to obtain a fine crystalline slurry and one the reaction mixture is heated to reflux and held for 18 gram of sodium ligninsulfonate and 16.8 grams of sodium hours. The product is stirred at 15-20" C., filtered and bicarbonate are added. Upon dissolution of the sodium washed. A yield of 79 grams of product are obtained. It bicarbonate, 18 grams of aniline and 10 drops of piperihas the formula: dine are added and the mixture is heated to reflux and held N02 N02 and dyes cellulose acetate, polyester, and polyamide textile for 18 hours. The mixture is then cooled to 25 C., the material yellow shades of excellent sublimation fastness. mother liquor is decanted, 200 ml. of isopropanol are EXAMPLE 2 added and the mixture is heated to 80 C. The mixture is cooled to 15 C. to crystallize the dye which is then To a solution of 1 gram sod1um lignmsulfonate in 200 filtered, washed with water and dried. A yield of 53 grams ml. of water are added 52.1 grams of 3-nitro-4-chlorobenof yellow dye is obtained. It has the formula:

l CH3 NO: N 2

lellesulfonyl chloride y) grams of Sodium and colors cellulose acetate, polyester and polyamide texbicarbonate, and 14.8 grams of 1,2-propanediamine (protile material yellow shades of good sublimation fastness. pylenediamine) The mixture is heated to 65-7 0 C., held EXAMPLE 5 for two hours and cooled to 20 C. The mixture is then filtered and the filter cake is washed and slurried in 200 In 100 ml. of water are dissolved 5.8 grams of 1,6- ml. water. One gram of sodium ligninsulfonate, 16.8 hexanediamine and 16.8 grams of sodium bicarbonate. The grams sodium bicarbonate, 18 grams aniline and 10 drops mixture is heated to 40 C. and 27.1 grams of 3-nitro-4- piperidine are added. The mixture is then heated to reflux chlorobenzenesulfonyl chloride (90% assay) are slowly and held for 9 hours, filtered at 20 C., washed until the added. The heating is raised and held at 60-65 C. for two dye cake is alkali-free and dried. A yield of 57.5 grams of hours. The mixture is cooled to 15 C., filtered and the yellow dye is obtained. It has the formula: filter cake is washed with water and slurried in 40 ml. of Quit-Q4omn-on-om-rrnsmQrrn-Q l (EH2 N03 N01 It colors cellulose acetate, polyester, and polyamide textile water and 20 ml. of isopropanol. To the mixture there material yellow shades of good sublimation fastness. is added 4.2 grams of sodium bicarbonate, 9 grams of A aniline and 5 drops of piperidine. The mixture is heated EX M PLE 3 to reflux and held for 18 hours.. It is then cooled to 15 In 200 ml. of water are dissolved one gram of sodlum C., filtered, the filter cake is washed with water until alkaliligninsulfonate, 52.1 grams of 3-nitro-4-chlorobenzenefree and dried. A yield of 21.5 grams of yellow dye is sulfonyl chloride (95% assay) and 16.8 grams of sodium obtained. It has the formula:

NO; NO,

bicarbonate. Then 14.8 grams of 1,3-propanediamine are and colors cellulose acetate, polyester, and polyamide added and the mixture is heated at -70 C. for two textile material yellow shades of good sublimation fasthours. The mixture is cooled to 20 C., filtered and the ness. filter cake is washed and slurried in 200 ml. of water. One The compounds described in the examples of the gram of sodium ligninsulfonate, 16.8 grams of sodium following table are prepared according to the procedures bicarbonate, 18 grams of aniline and 10 drops of piperidine employed in Examples 1 through 5. The compounds of a a ded and the 2 1113 is hea ed o efl x and held for the table give yelow dyeings exhib g ce lent tastness to sublimation on polyester fibers and conform to the formula:

TABLE 6 WXN, Du Pont) is stirred into the paste and the volume is brought to 500 ml. with warm water. This paste is Example No.

H 4-COOHs-2-Cl Since the novel compounds of the invention are waterinsoluble, they do not contain water-solubilizing substituents such as sulfo, carboxyl, salts thereof, etc.

The compounds of the invention can be used for dyeing hydrophobic fibers such as linear polyester, cellulose ester, polyamide, etc., fibers in the manner described in US. Pats. 2,880,050, 2,782,187, 2,757,064, and 3,043,- 827. The following procedure illustrates how the compounds can be applied to hydrophobic textile materials by the carrier dyeing technique.

EXAMPLE 25 An amount of 0.1 g. of the dye is dissolved in the dye pot by warming in 5 cc. of ethylene glycol monomethyl ether. A 2% sodium-N-methyl-N-oleyl taurate and 0.5% sodium ligninsulfonate aqueous solution is added, with stirring, until a fine emulsion is obtained. Water is then slowly added to a total volume of 200 cc. Then, 3 cc. of Tanavol (an anionic solvent carrier) are added and grams of a textile fabric made of poly (ethylene terephthalate) polyester fibers are entered. The fabric is worked 10 minutes without heat and then for 10 minutes at 80 C. The dye bath is then brought to the boil and held at the boil for one hour. Following this, the fabric is rinsed in warm water, then scoured in aqueous 0.2% soap, 0.2% soda ash solution. After scouring, the fabric is rinsed with water and dried.

When the compounds are used to dye polyamide textile materials, the above described procedure can be employed except the Tanavol dyeing assistant need not be used. In dyeing fiber of partially hydrolyzed cellulose acetate, the above procedure can be used, omitting the Tanavol carrier and carrying out the dyeing at 80 C.

As mentioned hereinbefore, the compounds of the invention possess excellent fastness to sublimation when applied to polyester fibers. The following example describes a typical procedure for dyeing polyester fibers by the heat fixation technique in which fastness to sublimation is an important property of the dye compound used.

EXAMPLE 26 Ten g. of dye, 10 g. of glycerin, 6 g. of sodium ligninsulfonate, and ml. of water are ground together in a ball mill. The paste is washed off the balls with 15 ml. of water. 3.5 g. of a nonionic surface active agent (Du Pont Compound No. 8-S) is added to 250 ml. of water at 190-200 F. To this solution is added slowly with stirring g. of the above dye paste, 125 ml. of a 2% solution of sodium alginate thickener (Keltex, Kelco Company) with stirring to produce an even paste. 0.25 g. of a sodium hydrocarbonsulfate wetting agent (Alkanol applied to a fabric consisting of poly(ethylene terephthalate) and 35% cotton fibers by means of a conventional padder. The fabric is then dried and, in open width, heated in an oven for seconds at 410 F. The fabric is then scoured at F. in a bath containing 0.2% of a nonionic emulsifier such as a polyoxyethylated fatty alcohol (Emulphor ON-870, General Aniline and Film Corporation) and 0.2% soda ash, rinsed and dried.

Polymeric linear polyester materials of the terephthalate type are illustrative of the linear aromatic polyester textile materials that can be dyed with the new compounds of the invention. Examples of such linear polyester materials are those prepared from ethylene glycol and dimethylterephthalate and those prepared from 1,4-cyclohexanedimethanol and dimethylterephthalate. Polyester textile materials prepared from 1,4-cyclohexanedimethanol and dimethylterephthalate are more particularly described in US. Pat. 2,901,446. Poly(ethylene terephthalate) fibers are described, for example, in US. Pat. 2,465,319. The polymeric linear polyester materials disclosed in US. Pats. 2,945,010, 2,957,745, and

2,989,363, for example, can be dyed. The linear aromatic polyester materials specifically named have a melting point of at least 200 C.

Examples of the polyamide fibers that can be dyed with the compounds of the invention are those consisting of nylon 66, made by the polymerizaiton of adipic acid and hexamethylenediamine, nylon 6, prepared from epsilonaminocaproic acid lactam, and nylon 8.

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described above and as defined in the appended claims.

I claim: 1. A compound having the formula IR R4 I l R-HN-SO2HN-R NHSOz--NHR l N02 N02 wherein R and R are the same or different and each represents a radical having the formula (XL. in which X represents hydrogen, lower alkyl, trifiuoromethyl, cyano, nitro, lower alkoxy, lower alkanoylamino, chlorine, bromine, lower alkylsulfonyl, lower alkoxycarbonyl, carbarnoyl, N-lower alkylcarbamoyl,

8. A compound according to claim 4 having the formula N,N-di-lower alkylcarbamoyl, lower alkanoyl, sulfamoyl, N-lower alkylsulfamoyl, N,N-di-lower alkyl- 9. A compound according to claim 4 having the formula sulfamoyl, lower alkylsulfonamido, or lower alkylthlo,

and n is 1, 2 or 3;

R represents alkylene of l to 6 carbon atoms, cyclohexylene, lower alkylcyclohexylene, cyclohexylenedi-loweralkylene, phenylene, or phenylene substituted with lower alkyl, lower alkoxy, or halogen; and

R and R are the same or different and each represents hydrogen or lower alkyl.

2. A compound according to claim 1 wherein R and R each represent the same radical and X represents hydrogen, lower alkyl, lower alkoxy, lower alkylsulfonyl, or nitro.

3. A compound according to claim 2 wherein R and R represent hydrogen.

4. A compound according to claim 1 having the formula 10. A compound having the formula NO: NO;

wherein R represents alkylene of l to 6 carbon atoms, phenylene, or phenylene substituted with lower alkyl, lower alkoxy or halogen;

R and R are the same or different and each represents wherein X represents hydrogen, lower alkyl, lower alkoxy chlorine or bromine, and m represents 2 m3.

5. A compound according to claim 4 having the formula 6. A compound according to claim 4 having the formula 7. A compound according to claim 4 having the formula 9 a radical having the formula References Cited UNITED STATES PATENTS 1,915,334 6/ 1933 Salzberg et a1. 260243 (Xh 2,075,359 3/1937 Salzberg et a1. 424250 in which X represents hydrogen, lower alkyl, trifluoro- 2258162 10/1941 Northey et 260 397'7 methyl, lower alkoxy, chlorine, bromine, lower HE J E E alkanoylamino, carbamoyl, sulfamoyl, N-lower alkyl- NRY IL Pfunary xalfuner carbamoyl, N,N-di-lower alkylcarbamoyl, N-lower D WINTERS, Asslstallt EXamlllel al-kylsulfamoyl N,N-di-1ower alkyl sulfamoyl and n 1 is 1 2, or 3; U.S. Cl. X.R. R and R are the same or different and each represents 8--1 C, 54.2, 178 R, 179, DIG. 4, DIG. 21; 260556 B hydrogen or lower alkyl. 

